Sulphur dyestuffs



the groupings ?atented Nov. I7, 1931 AQTES [PATENT 0m FRIEDRICH MUTE, or ELBERFELI), GERMANKYASSIGNOR 'ro GENERAL ,ANILINE WORKS, INC., OF NEW YORK, N. Y., A CORPORATION OF DELAWARE 'snrrnunnrnsrnrrs I No Drawing. Application i ile ddugu st" 30, 192S, Seria1 -No. 303,111, and'in fiermanyeseptember 15, 19 27.

dyestuffs dyeing violet to green shadeswhich dyes are obtainable by reacting withs'ulphur upon a compound of the"probablegeneral formula i I E l a wherein and B signify hydrogen, alkyl, aralkyl or aryl or stand jointly for one of -on, on,

Z represents hydrogen, alkyl,aralkyl or ar'yl, D and E stand for hydrogen one of the groupings andY stands for hydrogen orchlorine j The starting materials, havlng inf'thelr leuco form the above given probable general. formula, are obtainable by causing a com-.

P d of the general formula 2 wherein A, B, Z ,D,,E and Xhave the above mentioned signification, to be reacted upon I by p-aminophenol's, quinone-halogenim des' 0r p-nitrosophenols according to the. conditions usually employed for theip'roduction of blue colored alkaline solutions, which are or jointly for shades. j

easilyreduced" to the corresponding leucoindophenols, which latter are yellowish to brownish colored crystalline substances, easily soluble'in water, alcohol and sulphuric acid. The. alkaline solutions-0f the leuco in dophenols are easily re-oxidized, for instance by action of atmospheric oxygen to the corresponding indophenols.

Now Ihavefound that by submitting these I novel indophenolic compounds or their leuco 1 derivatives to a sulphur fusion novel sulphur colors are produced. The products obtained in both cases are substantially identical; when using the indophenolic' compounds these are presumably primarily reduced to the leuco indophenolic compounds in thesulphur melt. I'wish it therefore 'to be understood that the term indophenolior compound is used herein as genericfor both the indophenolic compounds and their leuco derivatives,

Theconditions of the sulphur fusion can be variedwithinwide limits without depart-- ing fromlthespirit of my'invention, I prefer, however, to use an alcoholic polysulphi d iu'sionL- 7 i :7 l 7 My novel sulphur dyestufi's are in. the dry an i state dark Violet to black powders, they are soluble in sodium sulphide solutions, from which cotton is dyed violet tovgreen shades exceedingly fastto light and boiling. They p can also be reduced to form hydrosulphite vats, from which cotton is dyed similar The following Emample 1. 294 parts by weightof the leuco indophenol from octo-hydro -naphtho quinoline and para aminophenol, of the forare boiled forabout hours under a reflux;

examples will illustrate my a invention without limiting it thereto condenser with 690 parts by Weight of calcined sodium sulphide and 830 parts by weight of sulphur with 1200 parts'by weight of alcohol with'the addition of 50 parts by weight of. copper sulphate. The alcohol'is then distilled oii after Water has been added to the reaetion mixture and the dyestuif which separates is filtered off. The residue is treated with suitable organic solvents capable of dissolving sulphur or it'is cleared from sulphur by means of the exactly calculated quantity of sodium sulphide; the dyestuilis then Washed and dried.

The dyestufi appears as a'dark powder and dyes cotton from a sodium sulphide or hydrosulpliite vat powerful yellowishgreen shades. The fastness to light and boiling is satisfactorv.

Example 2.293 parts by, weight ofthe leuco indophenol from octo-hydro-acridine and para-aminophenol, of the formula:

' 3 Dyestufls similar to those described in the other compounds than those especially mentioned in the examples whichfallwithin the scope of the probable general formula:

wherein A, B, Z, D, E, X and Y have the same signification .as given in the definition of the first formula.

As compounds of'thegeneral formula:

may be mention'edby way of example:

examples will be formed when starting from i means CH or and stands for hydrogen or chlorine.

. The complete dyestufis, formed of 'Name Formula thesecompouuds,

' yielding the following shades CH2 v i v GEa Tetrahydroquinoline blue to bleckblue NH m H: i o H,

Tetrahydroqumamine /CII3 blue to blackblue NH/ 2: I

H 0H3 8O r O I Tetrahydro- 1 v lepidine T blue to blackblue CH1 NH CII S5 I r 7 Tetrahydro-anaphthoquim agile (prefer- H bl h a y copper uis can and its salts- NH gt sulphate, sulphide.)

I claim 2- 1. Sulphur dyestuffs which in the dry state form violet to black powders, dyeing cotton from a sodium sulphide bath violetto green shades particularly fastto light and boiling, which are substantially identical with the products obtainable bysubmitting to a polysulphide fusion a compound having in its leuco form the probable general formula:

' l n it H X Ho W Y; IO/B D i l H whereinA and B signify hydrogen, alkyl, n aralkvl or-aryl or stand jointly for one of the groupings CH: CH:

f2. Sulphur dye'stu'ifswhich in the dry state;

form violet to black powders',- dyeing cotton from a sodium sulphide bath violet green shades particularlyfast to light and boiling, which are substantially identical with the products obtainable by submitting to apolysulphide fusion a compound having inits leuco, form the probable general formula:

wherein A and B signify hydrogen, alkyl or stand jointly for the grouping and X means CH or H CH3- 3. A new sulphur dyestufl' which in the dry state forms a black powder dyeing cot ton from a sodium sulphide bath powerful deep green shades particularly fast to light and boiling, which is substantially identical with the product obtainable by submitting to a polysulphi-de fusion the compound of the probable formula:

4. A new sulphur dyestuif which in the dry state forms a dark powder dyeing cotton from a sodium sulphide bath yellowish green shades particularly fast to light and boilin which is substantially identical with the pro uct obtainable by submitting to a polysulphide fusion the compound of theprobable my hand.

formula:

I5: OH-O-NH orn N i H1O H In testimonywhereof I have hereunto set FRIEDRICH MUflH. I211. 

